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Styrene
Polystyrene and Styrene Copolymers is a separate keyword.
Denis H. James, Dow Chemical, Freeport, Texas 77 541, United States
William M. Castor, Dow Chemical, Freeport, Texas 77 541, United States
1.
2.
3.
4.
4.1.
4.1.1.
4.1.2.
4.1.3.
4.1.4.
4.1.5.
4.2.
4.3.
Introduction . . . . . . . . . . . . . . .
Physical Properties . . . . . . . . . . .
Chemical Properties . . . . . . . . . .
Production . . . . . . . . . . . . . . . .
Catalytic Dehydrogenation of Ethylbenzene . . . . . . . . . . . . . . . . . .
Reaction Mechanisms . . . . . . . . . .
Adiabatic Dehydrogenation . . . . . .
Isothermal Dehydrogenation . . . . . .
Distillation of Crude Styrene . . . . . .
Oxidative Hydrogen Removal . . . . .
Styrene Propylene Oxide Process .
Styrene from Butadiene . . . . . . . .
1
2
3
4
4
4
5
5
7
7
7
9
1. Introduction
Styrene [100-42-5], also known as phenylethylene, vinylbenzene, styrol, or cinnamene,
C6 H5 CH=CH2 , is an important industrial unsaturated aromatic monomer. It occurs naturally
in small quantities in some plants and foods. In
the nineteenth century, styrene was isolated by
distillation of the natural balsam storax [1]. It
has been identied in cinnamon, coffee beans,
and peanuts [2], and it is also found in coal tar.
The development of commercial processes
for the manufacture of styrene based on the
dehydrogenation of ethylbenzene [100-41-4]
( Ethylbenzene) was achieved in the 1930s.
The need for synthetic styrene butadiene rubber ( Rubber, 3. Synthetic, Chap. 2.1.) during World War II provided the impetus for
large-scale production. After 1946, this capacity became available for the manufacture of a
high-purity monomer that could be polymerized to a stable, clear, colorless, and cheap plastic ( Polystyrene and Styrene Copolymers).
Peacetime uses of styrene-based plastics expanded rapidly, and polystyrene is now one of
the least expensive thermoplastics on a cost-pervolume basis.
4.4.
4.5.
5.
6.
7.
8.
8.1.
8.2.
8.3.
8.4.
8.5.
9.
10.
10
10
10
10
11
12
12
13
14
14
15
15
16
Styrene itself is a liquid that can be handled easily and safely. The activity of the vinyl
group makes styrene easy to polymerize and
copolymerize. When the appropriate technology became available through licensors styrene
was quickly transformed into a bulk-commodity
chemical, growing to a world-wide capacity estimated at 17106 t/a in 1993 and 18x106 t/a in
1995 [54]. For reviews of this important industrial history see [3], [4].
2. Physical Properties
Styrene is a colorless liquid with a distinctive, sweetish odor. The most important physical properties of styrene are summarized below.
Data appearing in the literature are not always
consistent, varying as a consequence both of the
method of measurement and the purity of the
monomer. Most manufacturers make available
the physical properties they regard as valid [5].
Important general physical properties of styrene
monomer are as follows:
Mr
bp
fp
104.153
145.15 C
30.6 C
Styrene
Critical density, Dc
Critical pressure, Pc
Critical temperature, T c
Critical volume, V c
Flammable limits in air
Flash point, Tag Closed Cup (TCC)
Autoignition point
Heat of combustion, H c , constant
pressure (25 C)
Heat of formation, H f
gas (25 C)
liquid (25 C)
Heat of fusion, H m
Heat of polymerization, H p (25 C)
Heat of vaporization, H v
(25 C)
(145 C)
Volume expansion coefcient
(20 C)
(40 C)
Q value
e value
Volume shrinkage on polymerization,
typical
Solubility of oxygen (from air)
(15 C)
(25 C)
(35 C)
All reactants and products are gases.
0.297 g/mL
3.83 MPa
362.1 C
3.37 mL/g
1.1 6.1 vol %
31.1 C
490 C
4.263 MJ/mol
Temperature,
147.4 kJ/mol
103.4 kJ/mol
11.0 kJ/mol
69.8 kJ/mol
0
10
25
50
Water in styrene
Styrene in water
0.02
0.04
0.07
0.12
0.018
0.023
0.032
0.045
421.7 J/g
356.7 J/g
9.783104 C1
9.978104 C1
1.0
0.8
17.0 %
53 mg/kg
50 mg/kg
45 mg/kg
Important parameters for monitoring the production and use of styrene are the refractive index and the density (Table 2). Table 3 lists supplementary physical properties of styrene.
Antoine equation:
log10 P = [6.08201 1445.58/ (209.43 +T )]
0
20
25
30
60
100
Refractive index, nD
Density, g/mL
0.9223
0.9050
0.9007
0.8964
0.8702
0.8355
1.54682
1.54395
1.54108
nD = 1.55830 0.000574 T
C
mPa s
tension,
mN/m
0
20
40
60
80
100
1.6367
1.6907
1.7489
1.039
0.762
0.588
0.469
0.385
0.324
34.5
32.3
30.0
27.8
25.6
23.5
3. Chemical Properties
The most important reaction of styrene is
its polymerization to polystyrene, but it also
copolymerizes with other monomers. The copolymerization with butadiene to give Buna S
synthetic rubber (emulsion styrene butadiene
rubber, E-SBR) was the reaction that led initially
to the development of the styrene industry. Other
characteristic reactions are described below. The
literature has been well summarized [3], [6], [7].
Oxidation of styrene in air is of special importance. The reaction leads to high molecular mass
peroxides by way of free radicals. Styrene is also
Styrene
oxidized to various other compounds, including
benzaldehyde, formaldehyde, and formic acid.
Other typical alkene reactions are observed with
stronger oxidizing agents:
Styrene can undergo addition to the double bond of the side chain as well as substitution in the ring. Treatment with bromine in
the cold gives addition, leading to styrene dibromide. This crystallizes well, and has been used
both to characterize styrene and to determine it
quantitatively in solution [8]. Splitting off hydrogen bromide from styrene dibromide gives
-bromostyrene, while phenylacetylene can be
formed by heating with calcium oxide. Addition of chlorine forms styrene dichloride, which
can be converted to - chlorostyrene and chlorostyrene by elimination of hydrogen chloride.
The halohydrins are important intermediates
in preparative chemistry. They react with alkali
to form styrene oxide, while further hydrolysis
leads to phenyl glycol. Iodohydrin is formed
from styrene in the presence of iodine, mercury(II) oxide, and water. 1-Phenylethanol is
an important intermediate product in the perfume industry ( Flavors and Fragrances). It is
formed by the hydration of styrene via quantitative addition of mercury(II) acetate:
Styrene forms solid complexes with copper and silver salts at low temperature. These
compounds are suitable for the purication of
styrene, or for separating styrene from mixtures
with other hydrocarbons. The color of the copper complexes makes this metal and its alloys
unsuitable for use in contact with styrene.
Styrene also undergoes many cyclization reactions [7]; e.g.:
Styrene
4. Production
Production of styrene is world-wide, and dates
back more than 50 years. However, new variations on established processes are continually being developed, and new companies are
building plants or buying out older producers.
The feedstock for all commercial styrene manufacture is still ethylbenzene ( Ethylbenzene).
This is converted to a crude styrene that requires
nishing to separate out the pure product.
The problem with carbon production is that carbon is a catalyst poison. When potassium is incorporated into the iron oxide catalyst, the catalyst becomes self- cleaning (through enhancement of the reaction of carbon with steam to give
carbon dioxide, which is removed in the reactor
vent gas).
C + 2 H2 O CO2 + 2 H2 H = 99.6 kJ/mol
Typical operating conditions in commercial reactors are ca. 620 C and as low a pressure
as practicable. The overall yield depends on
the relative amounts of catalytic conversion to
styrene and thermal cracking to byproducts. At
equilibrium under typical conditions, the reversible reaction results in about 80 % conversion of ethylbenzene. However, the time and
temperature necessary to achieve equilibrium
give rise to excessive thermal cracking and reduced yield, so most commercial units operate
at conversion levels of 50 70 wt %, with yields
of 88 95 mol %.
Dehydrogenation of ethylbenzene is carried
out in the presence of steam, which has a threefold role:
1) It lowers the partial pressure of ethylbenzene, shifting the equilibrium toward styrene
and minimizing the loss to thermal cracking
2) It supplies the necessary heat of reaction
3) It cleans the catalyst by reacting with carbon
to produce carbon dioxide and hydrogen.
Many catalysts have been described for this
reaction [9]. One catalyst, Shell 105, dominated
the market for many years, and was the rst to include potassium as a promoter for the water-gas
reaction. This catalyst is typically 84.3 % iron as
Fe2 O3 , 2.4 % chromium as Cr2 O3 , and 13.3 %
Styrene
potassium as K2 CO3 . It has good physical properties and good activity, and it gives fair yields
[10].
More recently, increasing competition has
promped manufacturers to seek new catalysts
that produce higher yields without compromising activity or physical properties, or catalysts that meet specic requirements. The SudChemie Group, which includes Nissan Girdler
Catalyst in Japan, Sud-Chemie in Germany, and
United Catalysts (UCI) in the United States, now
has the major share of the catalyst market with
its G-64 and G-84 types [11]. Shell also remains
active through a joint partnership with American Cyanamid called Criterion Catalyst. In addition to Criterion 105, a series of new Criterion
catalysts is available, including C-115 and C025 HA. Dow Chemical and BASF manufacture
their own catalysts to suit their specic needs,
and there are other small producers as well. A
catalyst life of ca. two years is claimed.
4.1.2. Adiabatic Dehydrogenation
Over 75 % of all operating styrene plants carry
out the dehydrogenation reaction adiabatically
in multiple reactors or reactor beds operated in
series (Fig. 1). The necessary heat of reaction is
applied at the inlet to each stage, either by injection of superheated steam or by indirect heat
transfer.
Fresh ethylbenzene feed is mixed with recycled ethylbenzene and vaporized. Dilution steam
must be added to prevent the ethylbenzene from
forming coke. This stream is further heated by
heat exchange, superheated steam is added to
bring the system up to reaction temperature (ca.
640 C), and the stream is passed through catalyst in the rst reactor. Adiabatic reaction drops
the temperature, so the outlet stream is reheated
prior to passage through the second reactor. Conversion of ethylbenzene can vary with the system, but is often about 35 % in the rst reactor
and 65 % overall. The reactors are run at the lowest pressure that is safe and practicable. Some
units operate under vacuum, while others operate at a low positive pressure. The steam: ethylbenzene ratio fed to the reactors is chosen to
give optimum yield with minimum utility cost.
The reactor efuent is fed through an efcient
heat recovery system to minimize energy con-
1%
2%
32 %
64 %
1%
Styrene
The separation of these components is reasonably straightforward, but residence time at elevated temperature needs to be minimized to reduce styrene polymerization. At least three steps
are involved. Benzene and toluene are removed
rst, and either sent to a toluene dehydrogenation plant or further separated into benzene for
recycling and toluene for sale. Ethylbenzene is
then separated and recycled to the reactors. Finally, styrene is distilled away from the tars and
polymers under vacuum to keep the temperature
as low as possible. Figure 3 A shows a typical
distillation train. The variant shown in Figure 3 B
is the Monsanto approach, where the major split
is accomplished rst, followed by separation of
the benzene toluene mixture.
Styrene
of trays [16], [17]. This results in less pressure drop, giving a lower bottom temperature,
shorter residence time, and hence less polymer
( 12. Energy Management in Chemical Industry, Chap. 6.6., 12. Energy Management in
Chemical Industry, Chap. 7.). Sulzer has done
pioneering work in the eld of packings for distillation [18]. Koch, Norton, and Glitch also produce packings for this purpose.
A polymerization inhibitor (distillation inhibitor) is needed throughout the distillation
Styrene
train. Sulfur was originally used, but environmental constraints make sulfur tar unacceptable
as a fuel. Many new inhibitors have been marketed, usually aromatic compounds with amino, nitro, or hydroxy groups (e.g., phenylenediamines, dinitrophenols, and dinitrocresols).
Uniroyal is especially active in this eld. The
distillation inhibitor tends to be colored and
is thus unacceptable in the nal product; nished monomer is usually inhibited instead with
tert-butylcatechol (TBC) (10 50 mg/kg) during storage and transportation.
Styrene
This reaction is exothermic, and can be accomplished either thermally or catalytically. Thermal processes [22], [23] require a temperature
of ca. 140 C and a pressure of ca. 4 MPa.
The thermal approach is most suitable for use
with puried butadiene. Yields of VCH are ca.
90 %. The catalytic process is based on nitrosyl halide iron complexes, and operates at
0 80 C and 0.1 1.30 MPa [24], [25]. The
yield is almost quantitative, and purication is
not difcult. This route can accept either the
raw C4 stream from a naphtha or gas-oil steam
cracker, or puried butadiene.
VCH is then dehydrogenated to ethylbenzene [26], [27] or, under more severe conditions,
oxidatively dehydrogenated directly to styrene
[28], [29]:
C6 H9 CH=CH2 C6 H5 CH2 CH3 C6 H5 CH=CH2
10
Styrene
Purity, %
Color, Pt Co, max.
Aldehydes, mg/kg
Peroxides, mg/kg
Polymer, mg/kg
Inhibitor, mg/kg
Impurities
ASTM
D 2827-92
Typical
analysis
ASTM
method
99.7
10
200
100
10
10 15
99.8
7
30
5
0
12
D 3799
D 1209
D 2119
D 2340
D 2121
D 4590
D 5135
By freezing point.
By gas chromatography.
distillation column. -Methylstyrene, isopropylbenzene (cumene), n-propylbenzene, and minor amounts of ethyltoluene and vinyltoluene
in nished styrene are a function of the separation power of the styrene still. Xylene content
is inuenced by the purity of the feed ethylbenzene. Phenylacetylene is produced by the
dehydrogenation process in amounts depending
on the catalyst used, typically 50 150 mg/kg.
Phenylacetylene must be removed by a hydrogenation step; it is absent from material made by
the styrene propylene oxide process.
Styrene
is 15 mg/kg. The solubility of oxygen from the
air in styrene monomer is 50 mg/kg. To prevent the occurrence of hazardous polymerization, styrene should always be kept cool, and
appropriate inhibitor and oxygen levels should
be maintained.
Styrene in storage is frequently padded with
inert gases, which are partially soluble in the
monomer. The consequences of desorption of
these gases must be considered in subsequent
handling. When the oxygen level in the inert gas
pad is < 8 vol %, the possibility of re or explosion is eliminated.
Storage and shipping containers for styrene
may be of standard steel or aluminum. Rust acts
as a catalyst for the polymerization of styrene,
so inorganic zinc linings are recommended for
storage tanks. Copper and brass ttings must be
avoided because they can lead to discoloration
of the styrene. Contamination with bases must
also be avoided, as these react with the inhibitor,
making it ineffective. Loading on a common carrier in a compartment next to a heated product
is an unacceptable practice.
Foam is the preferred medium for ghting
styrene res. Water fog dissipates vapor clouds
and provides cooling for structural supports, but
rarely extinguishes the re. Styrene monomer,
with its high volume resistivity, can acquire
and hold a static electric charge during transfer. Effective grounding measures must therefore be taken to eliminate uncontrolled electric
discharge.
11
1993
35 %
27 %
16 %
7%
5%
5%
4%
1%
1995
34 %
23 %
6%
2.2 %
3.3 %
40 %
24 %
13 %
11 %
7%
5%
12
Styrene
PMS [627-97-9] to differentiate it from the original mix. The VT mix was originally developed
to compete with styrene, with the idea that its
feedstock (toluene) would give it a competitive advantage over a benzene-based material.
However, benzene remained cheap and available, and VT proved to be more costly to make
than styrene, so it has not gained a large market
share. It has nevertheless maintained a specialty
position because of its unique properties. Table 5
lists the physical properties of VT and PMS.
8. Related Monomers
8.1. Vinyltoluene
Vinyltoluene, [25013-15-4] p-methylstyrene,
CH3 C6 H4 CH=CH2 , is a specialty monomer,
with properties similar to those of styrene [38].
It is available commercially in two different isomer mixes. For many years it has been supplied
as a 68/32 mixture of the meta and para isomers, reecting the composition of the feedstock ethyltoluene (ethylmethylbenzene), from
the Friedel Crafts synthesis ( Hydrocarbons,
Chap. 3.6.). This is usually called vinyltoluene
(VT). The advent of a para-specic route to
ethyltoluene using zeolite technology has made
available a 97 % para-isomer product called
Mr
bp, C
fp, C
Flammable limits, vol % in air
Flash point, TCC, C
Autoignition point, C
Heat of polymerization, H p ,
kJ/mol (25 C)
Heat of vaporization, H v ,
J/g (25 C)
Density, g/mL (25 C)
Refractive index, n25
D
Specic heat capacity (liquid),
1 1
K
(20 C)
Jg
Viscosity, mPa s (25 C)
Surface tension, mN/m (25 C)
Solubility in water, mg/kg (25 C)
VT
PMS
118.18
171.2
77
118.18
170.0
34
1.1 5.2
52.8
575
70
70
426.1
0.8930
1.5395
1.715
410.9
0.8920
1.5408
0.79
31.0
90
0.79
34.0
Styrene
product. The monomer is stored under refrigeration at 10 C, and it is typically inhibited with
TBC (12 mg/kg) during storage and transportation.
Toxicologically, VT has been considered to
be very similar to styrene, and normal precautions should be taken when handling it (see
Chap. 9). The ACGHI TLV is 50 mg/kg. VT is
ammable, but its vapor pressure does not produce a ammable mixture in air below 38 C.
It polymerizes more rapidly than styrene, and
polymerization can be initiated by exposure to
strong acids, peroxides, perchlorates, or hypochlorites. Contact between vinyltoluene and a
base will remove the TBC inhibitor.
Vinyltoluene is used in copolymers and as
a specialty monomer in paint, varnish, and
polyester formulations.
8.2. Divinylbenzene
Divinylbenzene
(DVB)
[1321-74-0],
C6 H4 (CH=CH2 )2 , is a cross-linking agent that
improves polymer properties. The commercial
monomer is mainly a mixture of m- and p-DVB
(typical ratio 2.25 : 1), diluted with ethylvinylbenzenes. Physical properties of the 55 % commercial mixture are listed below:
Mr
bp
fp
Pseudocritical pressure
Pseudocritical temperature
Flammable limits in air
Flash point, TCC
Autoignition point
Heat of vaporization, H v
(195 C)
Vapor pressure
(100 C)
(140 C)
(180 C)
Density (25 C)
Refractive index, n25
D
Surface tension (25 C)
Viscosity (25 C)
Solubility
DVB in water (25 C)
Water in DVB (25 C)
130.191
195 C
45 C
2.462 MPa
369 C
0.8 5.5 vol %
65.6 C
505 C
350.6 J/g
4.4 kPa
20.0 kPa
67.0 kPa
0.9084 g/mL
1.5585
32.1 mN/m
1.007 mPa s
0.0052 %
0.054 %
13
8.3. -Methylstyrene
-Methylstyrene
(AMS)
[98-83-9],
C6 H5 C(CH3 )=CH2 , is a monomer with a polymerization rate much lower than that of styrene.
It can be produced commercially by the dehydrogenation of isopropylbenzene (cumene),
but also occurs as a byproduct in the manufacture of phenol and acetone via the cumene
oxidation process, now the major source of
AMS ( Acetone, Chap. 4.1.; Hydrocarbons,
Chap. 3.8.). Physical properties of AMS are
listed below:
Mr
bp
fp
118.18
165 C
23.2 C
14
Styrene
Critical density
Critical pressure
Critical temperature
Critical volume
Flammable limits in air
Flash point, Cleveland
Open Cup (COC)
Heat of polymerization
Heat of vaporization, H v
(25 C)
(165 C)
Specic heat capacity (liquid)
(20 C)
(100 C)
Specic heat capacity (vapor) (25 C)
Solubility
AMS in water (25 C)
water in AMS (25 C)
Density (20 C)
Viscosity (20 C)
0.29 g/mL
4.36 MPa
384 C
3.26 mL/g
0.7 3.4 vol %
57.8 C
39.75 kJ/mol
404.6 J/g
326.4 J/g
2.047 J g1 K1
2.176 J g1 K1
1.2357 J g1 K1 ,
0.056 %
0.010 %
0.9106 g/mL
0.94 mPa s
AMS undergoes reactions and polymerizations similar to those of styrene and vinyltoluene. However, the addition of an -methyl
group to the side chain changes its chemical reactivity. AMS monomer tends to be more stable
than other vinyl aromatics. Homopolymers are
best prepared by ionic catalysis, copolymers by
radical polymerization.
Toxicologically, AMS is similar to styrene
(Chap. 9). The ACGIH TLV is 50 mg/kg, and the
STEL 100 mg/kg. AMS has a higher ash point
than styrene, and it is less likely to polymerize in
storage. It forms low molecular mass polymers
slowly after the depletion of oxygen and/or inhibitor. The polymer thus formed is usually a
viscous liquid. Uninhibited AMS in storage oxidizes slowly to acetophenone, aldehydes, and
peroxides, which may affect the polymerization
rate.
Homopolymers of AMS are used as plasticizers in paints, waxes, and adhesives. The
monomer is also used to form a copolymer with
methyl methacrylate. The copolymer has a high
heat-distortion temperature, and has been approved for use in food applications. Its light color
makes it useful in modied polyester and alkyd
resin formulations.
8.4. Chlorostyrene
The two compounds ortho- and para- chlorostyrene [2039-87-4], ClC6 H4 CH=CH2 , are reactive monomers produced only in small quantities. The para isomer has a boiling point of
152.62
98.9 C
229 C
26 to 42 C
104.4 C
610 620 C
10.04 kJ/mol
334.0 J/g
0.422 kJ/mol
730 mg/kg
Styrene
on the chloromethyl group, either before or after
polymerization. The chemistry of VBC has been
covered in an excellent review [39].
15
16
Styrene
10. References
1. E. Simon, Justus Liebigs Ann. Chem. 31
(1839) 265.
2. D. H. Steele, MRI Project No. 6450, Midwest
Research Institute, Kansas City, Mo., 1992.
3. R. H. Boundy, R. F. Boyer, (eds.): Styrene, Its
Polymers, Copolymers and Derivatives,
Reinhold Publ. Co., New York 1952; reprinted
by Hafner Publishing Corp., Darien, Conn.,
1970.
4. R. F. Boyer: Anecdotal History of Styrene and
Polystyrene, in R. Semour (ed.): History of
Polymer Science and Technology, M. Dekker,
New York 1982.
5. Dow Chemical, The Dow Family of Styrenic
Monomers, Form No. 115-00 608-1289 X-SAI,
Midland, Mich. 1989.
6. W. S. Emerson, Chem. Rev. 45 (1949) 183 ff.
7. K. E. Coulter, H. Kehde, B. F. Hiscock in E. C.
Leonard (ed.): High Polymers,
Wiley-Interscience, New York, vol. XXIV,
Vinyl and Diene Monomers, part 2: Styrene
and Related Monomers, 1971.
8. K. Meinel, Justus Liebigs Ann. Chem. 510
(1934) 129.
9. D. L. Williams, Styrene Catalysts, Past
Present and Future, AICHE Spring Meeting,
New Orleans, March 1988.
10. Shell Chemical, Technical Bulletin on Shell
005, Shell 105 Dehydrogenation Catalysts,
78 : 14 Houston, Texas 1978.
11. United Catalysts Inc., G-64 & G-84 Product
Bulletin, 2nd ed. Louisville, Ky. 1987.
12. Ullmann, 4th ed., 22, 298.
13. Lurgi, Low Energy Concept for Styrene
Production, Technical Brochure 2173 e/4.89.
14. Union Carbide Corp., US 3 282 576, 1966.
15. J. C. Frank, G. R. Geyer, H. Kehde, Chem.
Eng. Prog. 65 (1969) no. 2, 79.
16. Facelift for Distillation, Chem. Eng. 1987,
March 2, 14.
17. D. B. McMullen et al., Chem. Eng. Prog. 87
(1991) no. 7, 187.
18. Sulzer Bros. Inc., GB 1 020 190, 1966.
19. UOP Inc., US 4 435 607, 1984 (T. Imai).
20. K. Egawa et al., Aromatics 43 (1991) 5 6.
21. ARCO Chemical, Construction Permit
Application for Propylene Oxide/Styrene
Monomer Facility, Channelview, Texas, Texas
Air Control Board Account No. HG-1575 W,
July 1989.
22. Phillips, US 4 117 025, 1978 (T. C. Liebert,
W. A. McClintock).
23. Exxon, US 2 943 117, 1960 (A. H. Gleason).
Styrene
49. N. A. Brown, Reproductive Toxicol. 5 (1991)
3.
50. D. P. Boyd et al., SIRC Review 1 (1990) 5 23.
51. Z. Bardodej, E. Bardodejova, Amer. Ind. Hyg.
Assoc. J. 31 (1970) 206.
52. D. H. Steele et al., J. Agric. Food Chem. 42
(1994) 1661.
17